Process for synthesizing hydrocarbons



y 5, 1949- F. J. JENNY EIAL 2, 74,845

PROCESS FOR SYNTHESIZING BYQROQARBONS I Filed Sept. 12, 1944 sriqu firm/mm? 9 x5000)? I 'nscqm-wy rum/r EIOWER 1 INVENTORS UNI-TED A STAT P.ama July 5, 949

.raocss's Fon SYNTHESIZTNG' v mnocannons Frank J. Jenny, New York, Y., and Earl 'w. I

Rlbiett, Tenafly, N. 1., .auignors to Hydrocarbon Research, Inc., NewIoi-lr, N. Y. I

Application September 12, 1944, serial No. 553,750 1 The invention is directed to the synthesis of hydrocarbons through the reactions of carbon monoxide and hydrogen, and more particularly to thesynthesis of'liquid hydrocarbons of the type adaptable for use as a motorfuel such as gasoline.

Since the early investigation of the process for the hydrogenation o'f'carbon monoxide as dis- 5 Claims. (erase-449.0

closed, for example, in U. S. Patent No. 1,746,464 I to Fischer and 'Iropsch, attention has been focused on the prime problem of removing the considerable quantities of exothermic energy of the reaction. This. problem is all the more difficult when it is realized that the temperature must not vary substantially from a predetermined operating temperature. An increase in temperature of as little as 5 to F. may affect the product distribution adversely and result in. an increase in the rate of reaction so that a vicious circle of rising temperature is initiated. As the temperature climbs, the reaction shifts to the synthesis of methane and other undesirable products with consequent lowering of the yield of the more valuable liquid hydrocarbons.

Numerous processes have been proposed to overcome these and attendant difflculties, but, to

our, knowledge, none have been found satisfac- ..tory for operationin large-scale equipment or feasible from theviewpoint ofeconomics. I

A prime object of our invention is to provide a novel and simple process for reacting carbon monoxide and hydrogento form liquid hydrocarbons. e

Another. principal object is to provide a synthesis process which is both operable and practical in large-scalecommercial plants.

A further'obiect is to control the reaction temperaturein an easy but eil'ective manner.

Still another object is to conduct the hydrocarbon synthesis in a minimum of equipment tive thermal control. Our process involves passing synthesis gas, 1. e., carbon monoxide and hydrogen, under reacting and fluidizing ,co'ndi tions through a mass of powdered catalyst pre pared fromnietals of the iron group, preferably 1 iron, ltself, withdrawing andpcooling the reaction gases to separate a liquid fraction; and injecting the liquid fraction into the mass of. powdered catalyst to maintain good fluidization and to eflect close temperature control. The reaction gases which remain uncondensed at the stage" where the liquid fraction is taken for recycling to the reactor proceedto a recovery plant in.

which desired products are collected by conventional fractionation procedures.

The technique of fluidization which has gained prominence in the petroleum industry as a method for conducting reactions between gases and finely divided solids has been broadly suggested for various other reactions, e. g., the conversion of coal to gas. It'will be noted that in such operations as petroleum cracking and coal gasiflcation, the materialjundergoing processing yields increased volumes of gas in the reaction zone. The conversion of synthesis gas to hydrocarbons,on the other hand, leads to a substantial contractionof the order of in the volume of gas as it passes up through the reactor. This is very detrimental to-the operation of a densephase fluid system.

While in U. 5. Patent 1,984,380 directed to a fluid process of producing chemical reactions,

Odell proposes the synthesis of hydrocarbons by the passage of mixtures of hydrogen and carbon monoxide through a mass of fluidized particles of iron-copper catalyst, he does not suggest how proper fluidization of the catalyst mass is to be attained in spite of the substantial contraction of the gases flowing through the mass. Furthermore, Odell teaches that increasing the velocity of the fluid decreases the time and the intimacy of its contact with the catalyst and therefore decreases the amount of' reaction and the tem-' perature rise. From the chemical engineering point of view such a method of temperature regulation is distinctly undesirable and ineflicient. Also, recourse to a high gas velocity is fundamentally at cross purposes with the fluidization technique which is especially designed to enhance the intimacy of contact between gases and finely divided solids. Alternatively, Odell discloses that the temperature may be controlled by circulating the fluidized catalyst through a cooling system. The removal of heat from this highly exothermic synthesis by circulation of the heavy mass of catalyst would involve the expenditure of considerable energy. 1 In our process, cooling by the recycling of liquid to the reaction zone involves an expenditure of energy equivalent to that required by Odell for cooling the catalyst after it is withdrawn from the reaction zone. Accordingly, our process enjoys a net gain equal to the energy that would be expended in circulating the catalyst Moreover, the circulation of catalyst necessitates more equipment and more catalyst and subjects both to high erosion.

By dense-phase fluidization, we mean passing gas or vapor up through a mass of powdered material at such a velocity that the powder becomes suspended in the gas but exhibits what has been termed hindered settling." While the gas velocity is sufficient to cause turbulence and seething of the powdered mass so that it reenough so that there is relatively little entrainsembles a boiling liquid, it is, nevertheless, low

ment of the powder in the gases discharging from mension of the reactor. Thus, in the vicinity of the bottom of the reactor where the synthesis gas is introduced, the catalyst mass is in a very fluid and turbulent state whichdiminishes as the reaction gases ascend until the upper portion of the mass of catalyst powder is comparatively quiescent. Because of the very low gas velocity in the upper portion of the mass, there is a tendency 4. hydrocarbon products are drawn as shown at It and residual noncondensable gases, chiefly carbon dioxide, are vented at H. Any desired proportion oi these gases may be returned to the generator (not shown) for the production of synthesis gas. Pump I2 is used to inject liquid hydrocarbons into the reactor through a multiplicityof valved inlets IS. The liquid is preferably atomized so that it is immediately converted to vapor within'the mass of fluidized catalyst. It will be noted that while the ascending reaction gas diminishes in volume along the vertical dimension of the reactor, the volume of the vapors from the injected liquid bydrocarbons increases so that a compensating effect is realized with the result that there is a fairly uniform rate of fluidization along the entire height of the reaction mass. This generally uniform condition of fluidity and turbulence permits the attainment of very sensitive thermal regulation, 1. e., variations of as little as 5 to 10 F. within the reaction mass are avoided. Moreover, good fluidization makes possible a relatively high rate of heat transfer from the reaction mass to'the cooling surface, represented as coil i4.

' Obviously, any improvement in the rate of heat transfer is translatable into a reductionin the portant consideration in commercial operations.

for the mass to'become deaerated, i. e., the catalyst mass tends to pack and form channels through which the gases escape without making proper contact with the catalyst. Marked temperature diiferences are observable in the upper and lower portions of the catalyst mass. It is as if the fluid reaction zone were divided into two portions having little mixing of their powdered masses. This tendency not only nullifies the prime purpose of employing fluidization, which is to maintain uniform temperature throughout the reaction zone, but also makes heat transfer to cooling surfaces disposed within the upper portion of the reaction mass very poor.

These operational obstacles are overcome and additional advantages realized when, as we have discovered, liquid hydrocarbons recovered from the reactionv gases are injected into the reaction zone and revaporized by contact withthe hot catalyst powder to provide suflicient gas to equalize fluidization and simultaneously to absorb substantial quantities of heat from the reaction zone.

To clarify further the'operation of our process, reference is made to a typical embodiment represented diagrammatically in the drawing attached to this specification.

Synthesis gas enters the reactor I through pipe 2 and passes up through a fluidized mass of powdered iron catalyst which has a pseudo-liquid level 3. The pseudo-liquid level is the region wherein the bulk of the reaction gases become disengaged from the comminuted catalyst prior to escape from the reactor.- The reaction gases carrying a limited quantity of catalyst powder In addition, the introduction and vaporization of liquid hydrocarbons provide a very convenient and practical procedure for removing considerable quantities of exothermic energy from the reaction zone. As a matter of fact, we have found that it is possible to choose operating conditions so that the entire heat of reaction may be borne out or the reactor by the reaction gases and vaporized liquid hydrocarbons. Under such conditions, the cooling coil H or other suitable heat exchange device within the reactor I may be eliminated. As shown in the drawing, a portion of the uncondensed reaction products are bled from pipe 8 and returned by way of pipe I5 and blower is to the reactor for the further conversion of residual carbon monoxide and hydrogen into hydrocarbon products. We prefer to pass these gases through a condenser in order to precipitate another fraction-of liquid hydrocarbons and to remove water of reaction prior to returning them through blower I to the reactor I. This permits the recycling of a greater proportion of the unconverted synthesis gas than is possible when the liqueilable hydrocarbon products and water 01' reaction are not removed from this stream. Alternatively, the recycle gas may be drawn from line ll after the various hydrocarbon products have been separated in the recovery plant 1. For the purposes of our invention, it is not necessary to recycle any gas at all proportion of catalyst powder which leaves the reactor by entrainment in the reaction gases is pulled down with the liquid hydrocarbons in separator 6 and the catalyst-oil slurry is pumped.

back to the reactor. If desired, a cyclone or other separator of very simple design may be placed at separated and withv the outlet of reactor l to the bulk of the entrained catalyst directly to the reactor: at the 1 catalyst remaining suspended in the reaction gases would be caught in separator I as has already been explained.

Further details of the processor our invention will be given}. by way of example, in terms of a.

'plantdesigned to produce daily 800 barrels of liquid hydrocarbons. The particular catalyst 'se-. lected for this plant is iron powder of which all passes through a 200-mesh screen and about 85% passes through a 325; mesh screen. The .latter fraction has a particle size distribution of'niairly broad range. ii The catalyst is substantially pure ironintowhich about 1.0% of potassium oxide (K and about 2.0% of alumina (A1203) have been mc rporated. as promoters. With a reactor 12 feet in diameter and a pseudo-liquid level about 30 feet above the bottom of the reactor, synthesis gas having a carbon-monoxide:hydrogen ratio of about'3z4 and a temperature of 550 F. is fed into the reactor at the rate of 32,000,000 cubic feet per day, Recycle gas at atemperature of 450 1''. is returned to the reactor at an equal rate of flow. This recycle gas has been passed through coolers and condensers which remove a considerableproportion'of the liquid hydrocarbon products and substantially all the water of reaction. Carbon monoxide and hydrogen are present in the recyclegas in the ratio ofwabout' 1:1. Liquid hydrocarbons at a temperature of about 600 F. are injected at a rate of 32,000 barrels per day into the fluid mass from evenly distributed points to prevent flooding of the catalyst with oil in any part of the reactor. The recycle cooling oil carries catalyst powder which has been transported foul; of the reactor by entrainment in the eiiluent gases. Heat exchange surfaces are disposed within the reactor to take up residual (about 50%) exothermic energy which is not removed by the reaction gases and vaporized recycle oil. The reactor generates heat at a rate of the order of 70,000,000 B. t. u. per hour. The synthesis is conducted at a pressure of 250 pounds per square inch and at a temperature of 600 F. Under these operating conditions, the gases flowing through the reactor have a linear velocity of about 1 foot tion and th'e'reby'to' yield different hydrocarbon products. Such promoters as compounds of alkali and-alkaline earth metals, the oxides of titanium and silicon, and salts of molybdenum and chromiummay be employed. Inasmuch as both components of synthesis gas, viz., hydrogen ahd car- I or compounds of metals of the iron group.

bon monoxide, are strong reducing agents, the

powdered catalystcharged to the reactor may be in the form of any readily reducible compoun The powdered catalyst used in our process is of such size or, more accurately stated, of such particle size distribution that, under the reaction conditions prevailing in they reactor, the gases l passing up through a bed of the powder will r'en-' derit 'fluid. While powders which are relatively 'coarse or relatively fine may be used in some cases,

we generally choose 200- to 400-mesh powders. Such powders; preferably have a predominant fraction, say 85%, passing through a 325-mesh screen and the particle sizes in this fraction are distributed over a fairly broad range. Instead i of pulverlzing the catalyst itself, the catalytic material may be deposited by known techniques on finely divided, inert supports like diatomaceous earth. Accordingly, powdered catalysts suitable for our fluid synthesis process embrace both the unsupported and the supported types.

A veryimportant feature'of the process of our invention is its great flexibility whlch'readily permits operating variations to yield various distributions of liquid hydrocarbon products. Thus, when a wax substitutes are in demand, the 'recy le oil may be fractionated so as to draw off any eavy,

wax-like products'which may be present. Under other circumstances, it may be desirable to recycle the heavier hydrocarbons since'these tend to be uct distribution may be altered to per second; with such a gas velocity there is sufilcient fluidity and turbulence of the catalyst mass so that temperature differences of as little as 5 to 10 Rare avoided and a satisfactory rate of heattransfer to thecooling surfaces is attained.

Besides, the quantity of. catalyst carried'out by entrainment and requiring replacement in the reactoris small. In'the foregoing, references to iron catalyst although catalysts of the other metals of the iron group, vlz., cobalt and nickel, are well suited to ourprocess and, in certain instances, may oiler some advantages over iron. The catalyst is predominantly, i. e., at least 80%, a metal or a mixture of metals of the iron groups We are, of course, aware thatvarious promoters and activators may beadded to .the iron group metals in'minorproportions, i. e., not morethan 20%, to modify the hydrocarbonsynthesis reacconverted in the reactor into lower boiling prod-'- nets and, accordingly, increase the yield of liquid hydrocarbons in the gasoline range." It is therefore clear that by simple fractionating means, interposed-in the recycle oil line, the final prods uit particular objectives. a

It is generally advisable to regenerate the catalyst at such rate, either periodically of continuously, as to maintain the catalyst in the synthesis "reactor at fairly constant andhigmactivity. This may be accomplished by treatingrthe catalyst which leaves the reactor by entrainment in the eilluent gases and is recovered as an oil slurry. Alternatively, catalyst powder may be drained from the reactor through a draw-off pipe having its inlet in the fluid reactor below the pseudoliquid level. In either case, .the withdr'awncatalyst'is treated, e. g., with hydrogen under fluidizing and reacting conditions, to remove any poisons or deactivating subtances deposited on the catalyst particles. When wax-like products accumulate on the catalyst particles, they maybe recovered by extracting the fouled catalystwith suitable solvent. After the catalyst is reviviiied I than 10%.

by extraction and/or other treatment, it is returned to the fluid reactor used for the synthesis of hydrocarbons. l A

By the term, 'liquid hydrocarbons, we mean hydrocarbon molecules of not less than .4- carbon atoms. The liquid recovered from our synthetic process may contain varying q antities of 085'- genated hydrocarbons such as alcohols, but these oxygenated compounds will usually amount to less methane, ethylene, etc., may, be recycled to the The noncondensable fraction of the reaction products, including carbon dioxide;

- What we claim is:

' 1. A process for effecting catalytic'hydrogenation of carbon monoxide by reaction with hydrogen during passage througha mass of fluidized powdered synthesis catalyst disposed in a vertical reaction zone wherein the catalyst is maintained 1 in a state of dense phase fluidization by the action of the gaseous fluldrising therethrough, the velocity of said gaseous fluid being sumciently low so that there is relatively little entrainment 01! said powdered catalyst in the gases discharging from,

said reaction zone, which comprises continuously introducing carbon monoxide and hydrogen as gaseous reactants to the lower portion of said zone lyst disposed in alvertical reaction zone wherein the catalyst is maintained in a state of dense phase fluidization by the action of the gaseous fluid rising therethrough, the velocity of'said gaseous fluid being sufllciently low so that there is relatively little entrainment of said powdered catalyst in the gases discharging from said reaction mne, which comprises continuously intros ducingcarbon monoxide and hydrogen as gaseous reactants to the lower portion of said zone at a predetermined rate, passing the so-introduced reactants upwardly through said mass at a temperature of about 600 F. and'under a pressure of about 250, pounds such that said reactants are weight with substantial volume contraction of said gaseous reactants as they proceed therethrough, injecting added vaporizable liquid into said reaction mixture at a plurality of succeeding.

points spaced apart in the direction of reactant .travel through the catalyst mass, and regulating the amount of vaporizable liquid injected so as to gaseous fluid rising therethrough, the velocity of,

said gaseous fluid being sufllciently low so that there is relatively little entrainment of said pow-' dered catalyst in the gases discharging from said reaction zone, which comprises continuously introducing carbon monoxide and hydrogen as] gaseous reactants to the lower portion of said zone 'at a predetermined rate, passing the so-intro-.

duced reactants upwardly through said mass under predetermined conditionsof temperature and pressure such that said reactants are substantially converted into hydrocarbons with substantial volume contraction of said gaseous reactants as they proceed therethrough, continuously removing from the reaction zone an eilluent stream comprising normally liquid. hydrocarbons, separating from said stream liquid hydrocarbons vaporizable under the conditions prevailing within said reaction zone, injecting so-separated hydrocarbons into said reaction mixture at a plurality of succeeding points spaced apart in the direction of reactant travel through the catalyst mass, and regulating the amount of hydrocarbons injected so as to compensate for said contraction and maintain substantially even fluidization of said catalyst along the vertical dimension of said reaction zone.

3. A process for effecting catalytic hydrogenation of carbon monoxide by reaction with hydrogen to produce hydrocarbons during passage through a mass of fluidized powdered ircn cata= substantially converted into hydrocarbons with substantial volume contraction ofsaid gaseousreactants as they proceed therethrough, continuously removing from the reaction zone an eiflu'ent stream comprising normally liquid hydrocarbons, separating from said stream liquid hydrocarbons vaporizable under the conditions prevailing within said reaction zone, injecting so-separated hydrocarbons into said reaction mixture at a plurality of. succeeding points spaced apart in the direction of reactant vtravel through the catalyst mass, and regulating the amount of hydrocarbons injected so as to compensate for said contraction and maintain substantially even fluidization of said catalyst along the vertical dimension of-said reaction zone. v

v 4. A process for effecting catalytic hydrogenation of carbon monoxide by reaction with hydrogen during passage through a mass of fluidized powdered synthesis catalyst disposed in contact with cooling. surfaces in a vertical reaction zone wherein the catalyst ismaintained in a state of dense phase fluidization by the action of the gaseous fluid rising therethrough, the velocity of said gaseous fluid being suinciently low so that there is relatively little entrainment of said powdered catalyst in the gases discharging from said 7 reactants upwardly through said mass under predetermined conditions of temperature and pressure such that said reactants are substantially converted into compounds of higher molecular weight with substantial volume contraction of said gaseous reactants as they proceed there-' through, injecting a vaporizable liquid into said reaction mixture at a plurality of succeeding points spaced'apart in the direction of reactant travel through the catalyst mass, and regulating the amountcf va'porizable liquid injected so as to compensate for-said contraction and to maintain a a substantially uniform linear velocity of gaseous flow of about 1 foot per second through said catalyst mass thereby promoting a uniformly high gaseous fluidrising therethrough, the velocity of said gaseous fluid being suiflciently low so that there is relatively little entrainment of said powdered catalyst in the gases discharging from said reaction zone, which comprisescontinuously introducing carbon monoxide and hydrogen as gaseous reactants to the lower portion of said zone at a predetermined rate, passing the so-intro duced reactants upwardly through said mass under predetermined conditions or temperature and pressure such that said reactants are substantially converted into hydrocarbons with substantial volume contraction of said gaseous reactants as they proceed therethrough, continuously removing from the reaction zone an eflluent l0 of gaseous flow of about 1 foot per second through said catalyst mass thereby promoting a uniformity high rate of heat transfer to the cooling surfaces in contact with said fluidized catalyst.

FRANK J. JENNY. EARL W. RIBLE'I'I.

REFERENCES CITED The following references are of record in the stream comprising normally liquid hydrocarbons, 1 fil of this patent;

UNITED STATES Pa'mm's Number Name Date 1,955,873 Deanesly Apr. 24, 1934 1,984,380 Odell Dec. 18, 1934 2,318,602 Duftschmid May 11, 1943 2,347,682 Gunness May 2, 1944 2,383,636 Wurth Aug. 28, 1945 2,406,851

Redcay Sept. 3, 1946 

